Documente Academic
Documente Profesional
Documente Cultură
Chunyu Zhou, Chunjie Yan, Qi Zhou, Hongquan Wang & Wenjun Luo
To cite this article: Chunyu Zhou, Chunjie Yan, Qi Zhou, Hongquan Wang & Wenjun Luo (2016):
Producing a synthetic zeolite from secondary coal fly ash, Environmental Technology, DOI:
10.1080/09593330.2016.1169320
Article views: 21
Download by: [University of Nebraska, Lincoln] Date: 13 June 2016, At: 21:11
ENVIRONMENTAL TECHNOLOGY, 2016
http://dx.doi.org/10.1080/09593330.2016.1169320
CONTACT Chunjie Yan chjyan2005@126.com Engineering Research Center of Nano-Geomaterials of Education Ministry, China University of Geosciences,
Lu Mo Road 388, Wuhan 430074, People’s Republic of China
© 2016 Informa UK Limited, trading as Taylor & Francis Group
2 C. ZHOU ET AL.
SCFA, the alkali leaching process was carried out under powder diffraction system with Cu Kα radiation operat-
certain vapor pressure in a high-temperature steam ing at 40 kV and 40 mA. Phase identification was per-
before the hydrothermal treatment, leading to a great formed by searching the ICDD powder diffraction file
shortening of processing time and improving of extrac- database, with the help of JCPDS (Joint Committee on
tion efficiency. Powder Diffraction Standards) files for inorganic com-
The current study investigated the fabrication of zeo- pounds. The morphology of the sample surfaces and
lites from secondary CFA, which is the residue from the the energy dispersive X-ray spectroscopy (FE-SEM/EDX)
extracting aluminum industry. The synthesis yield, analyses were examined on a Hitachi SU8010 field emis-
zeolite types and morphology have been systematically sion scanning electron microscope in powder samples
studied with respect to alkalinity, Al ion addition, crystal- coated with Au. Fourier-transform infrared (FT-IR)
lization time and temperature. The novelty of this work spectra measurements were performed on a Nicolet
comes from the use of low-activity secondary CFA AVATAR360 instrument using the standard KBr disk
residue, rather than the raw CFA. method. Whiteness measures were performed on a com-
mercial whiteness meter (WSB-3, Shanghai, China) using
pressed pellet samples.
2. Experimental design and methods
2.1. Chemicals and materials
2.4. Calcium ion exchange capacity measurement
The secondary fly ash was the residue from the extract-
ing aluminum industry by acid leaching method The calcium ion exchange capacity of synthesized zeolite
obtained from Junger power plant, Shenhua Group NaA was determined according to Chinese Light Industry
Zhungeer Energy Co., Ltd, which is used in this study Standard–Zeolite NaA for detergent (QB/T 1768-2003).
after a calcination treatment at 900°C for 2 h. Sodium The results were expressed as mg CaCO3/g of solids.
The detailed procedures are as follows. First, the prep-
Environmental Technology
Figure 1. (a) The flow chart of synthesis zeolite; (b) XRD pattern of the secondary CFA residue; SEM images of the secondary CFA residue (c),
activated material at 2 mol/L NaOH (d), synthesized zeolite NaA (e), and EDX spectra and chemical composition of the selected area (e1).
recorded when the solution turned from wine red to 3. Results and discussion
blue. Calcium ion exchange capacity was calculated by
3.1. Characterization of secondary CFA
the following equation:
From Table 1 it can be easily observed that the content of
100.08 × (50 × c0 − 10 × c1 × VE ) aluminum oxide in SCFA decreases to 26.25% from
E= , (2)
m × (1 − W) 51.72% in CFA, while the content of silica increases to
65.39% from 29.47%, leading to an increase in Si/Al
where E is the amount of calcium ion adsorbed (mg ratio from 0.48 to 2.12. The alumina extracting process
CaCO3/g), C0 is the concentrations of calcium chloride converted the Al-rich CFA to Si-rich SCFA. The XRD
standard solution (mol/L), C1 is the concentration of pattern as shown in Figure 1(b) reveals that quartz
EDTA standard titration solution (mol/L), VE is the (JCPDS card No. 85-1054) and mullite (JCPDS card No.
volume of EDTA standard titration solution consumed 83-1881) as the main crystalline mineral phase associ-
(mL), m is the mass of zeolite sample (g), W is the ated to anatase (JCPDS card No. 71-1168) as the impurity
amount of hygroscopic water (%) and 100.08 is the mineral phase in the SCFA sample. The presence of
molar mass of calcium carbonate (mg/mol). amorphous phases is identified by the presence of the
4 C. ZHOU ET AL.
broad diffraction peak (near 2θ = 22°). The particles of readily observed at 2.0 mol/L NaOH in Figure 2(b) and the
SCFA used in this study without regular shape and the particle size of the product is estimated to be 1–2 µm.
particle size ranges from about 0.5 to 10 µm, which can Therefore, the NaOH concentration of 2.0 mol/L is
be seen in Figure 1(c). regarded as the optimal alkalinity for zeolite NaA
synthesis.
The results above revealed that in the alkaline fusion
3.2. Effects on NaA zeolite preparation process not only the Si–Al-radical ions were depolymer-
3.2.1. Effect of alkalinity ized but also the zeolite grains were formed. What is
more, different alkalinity lead to different types of zeo-
The effect of alkalinity in the alkaline leaching process
lites, indicating that the alkaline fusion process is very
was studied at NaOH concentrations of 1.0, 2.0, 3.0 and
effective in extracting silicon and aluminum from SCFA
4.0 mol/L. Figure 1(d) represents the FE-SEM image of
and forming of new types of zeolites.
alkaline-activated material at 2.0 mol/L NaOH. It can be
clearly seen that the leached material is greatly different
from the raw material, the surface has become fluffy and 3.2.2. Effect of SiO2/Al2O3 molar ratio
made up of some tiny granules, leading to the result that The influence of SiO2/Al2O3 molar ratio on the crystalliza-
the crystal phases in SCFA has been damaged after the tion types of zeolite was investigated in this study. The
leaching process. contents of SiO2 and Al2O3 are given in Table 1, and
Environmental Technology
Figure 2(a) shows the XRD patterns of the products the molar ratio of SiO2/Al2O3 is calculated to be 4.2. In
obtained at different alkalinities. The typical diffraction order to obtain SiO2/Al2O3 mole ratios of 1.0, 1.8 and
peaks corresponding to quartz and mullite remarkably 3.0, 13.64 g, 5.72 g and 1.74 g of NaAlO2 were mixed
disappear from all the synthesized products, revealing with 10 g calcined SCFA in 100 mL 2 mol/L NaOH sol-
that the raw material could be dissolved in alkali solution ution, respectively.
either 1 or 4 mol/L. When the alkalinity in the system was Combined the results of XRD and SEM, it can be easily
set at 1 mol/L, besides the characteristic peaks of zeolite seen that when the molar ratio of SiO2/Al2O3 kept at 1.0,
NaA (JCPDS card No. 43-0142), zeolite NaP (JCPDS card zeolite NaP, zeolite NaA and sodalite were all formed.
No. 39-0219) also appears in the XRD pattern and When the molar ratio of SiO2/Al2O3 increased to 1.8,
becomes the main product. These results indicate that the XRD pattern is consistently in good agreement with
zeolite NaP1 tends to be synthesized in low alkaline con- NaA zeolite reference with JCPDS No. 43-0142, without
centration. With the increasing of alkalinity, pure-phase any other impurity peaks. Furthermore, the single-
zeolite NaA is obtained under NaOH concentration at phase chamfered-edge zeolite NaA sample in pure
2.0 and 3.0 mol/L. It is interesting to note that the form with a high crystallinity shown in Figure 3(c)
peaks of zeolite NaA decreased slightly and other proves that the pure zeolite NaA with good morphology
phase corresponding to hydroxysodalite (HS, Na4Al3Si3- has been successfully synthesized. However, apart from
O12(OH), JCPDS card No. 11-0401) was detected in the zeolite NaA, zeolite X is gradually increased while the
product obtained under NaOH concentration of 4.0 molar ratio of SiO2/Al2O3 increased to 3.0. Meanwhile,
mol/L. Similar trends could be observed in conventional without addition of other alumina source, single-phase
hydrothermal syntheses, where zeolite NaP was formed zeolite P is successfully obtained at the SiO2/Al2O3
at low alkaline concentrations and HS instead of zeolite molar ratio of 4.2, as shown in Figure 3(a). The results
A at high alkaline concentrations, since zeolite A is meta- reveal that without addition of NaAlO2 the zeolite NaA
stable and tends to transform thermodynamically to could not be synthesized, while the raw SCFA under
more stable phases. SiO2/Al2O3 mole ratio of 4.2 is suitable for zeolite NaP
In order to know which alkali concentration is better synthesis. Whereas, the morphology of zeolite NaP
for zeolite NaA synthesis, the FE-SEM technique is obtained at SiO2/Al2O3 mole ratio of 4.2 and 1.0 differs
applied to study the detailed morphologies of the two a lot. Figure 3(b) shows that the zeolite NaP presents
samples obtained at 2 and 3 mol/L NaOH solution, as wool ball-like shape with the size about 1.0–2.0 µm and
shown in Figure 2(b) and 2(c). Cubic crystalline structure each of them is isolated without aggregation. While
with well-defined edge of the NaA zeolite particles can be zeolite P in Figure 3(e) shows totally different
ENVIRONMENTAL TECHNOLOGY 5
Figure 2. (a) XRD patterns of the synthesized products obtained at different alkalinities; FE-SEM images of the synthesized products
obtained at different alkalinity 2.0 mol/L (b) and 3.0 mol/L (c).
morphology, the diamond shape with clear crystal edge samples crystallized from 0 to 8 h, which displays the for-
confirms that it is well crystallized. Similar observation mation process of zeolite NaA, as shown in Figure 4(b)–(e).
has been reported by Huo.[22] Without the crystallization process, the product presents
From the results showed above, it can be deduced in small spherical particles about 0.5 µm. As the crystalliza-
Environmental Technology
that the molar ratio of SiO2/Al2O3 is the key factor for tion time proceeded, the small spherical particles gradu-
forming different types of zeolites. Consequently, the ally grow to big cubic particles, and the well-defined
optimum molar ratio of SiO2/Al2O3 for obtaining zeolite edge of the NaA zeolite particles in 1.5–2.5 µm with
NaA by hydrothermal method is 1.8, as well different cubic crystalline structure was finally obtained at 8 h.
morphology zeolite P could be obtained by varying the
molar ratio of SiO2/Al2O3. 3.3.4. Effect of crystallization temperature
The effect of varying crystallization temperature was
3.3.3. Effect of crystallization time investigated after the aging process at 60°C for 12 h.
To investigate the influence of crystallization time on the Figure 5(a) presents the XRD patterns of the samples
structure of the products, the synthesis of zeolite NaA obtained at different temperatures. It clearly reveals
was carried out at various times. Figure 4(a) shows the that when the crystallization temperatures are fixed at
XRD patterns of the products obtained at different room temperature, 55°C or 75°C, both zeolites NaA and
times. All the samples were aged 60°C for 12 h before zeolite X appear in the XRD patterns. Furthermore,
crystallization. there is an obvious tendency that the peaks of zeolite
After the aging period without any crystallization X decreased slightly when the crystallization tempera-
time, the new peaks, which correspond to zeolite NaA, ture is raised from room temperature to 75°C, and
have started to form in the product and the peaks inten- finally disappear when the temperature reaches 95°C,
sity markedly increased as crystallization time increased only pure-phase zeolite NaA with high purity could be
to 8 h. It is obvious that the peaks of zeolite A decreased detected. Therefore, 95°C is chosen as the best crystalli-
noticeably and another phase corresponding to zeolite P zation temperature for synthesis of zeolite NaA. Previous
was detected in the products when the crystallization studies reported that zeolite could be synthesized at any
time is over 12 h, implying that the zeolite A once syn- temperature in the range of 60–300°C. The results of the
thesized in the suspension started to convert into the present study are in good agreement with Breck’s rec-
other phases as the crystallization proceeded. This is ommendation that crystallization temperature ca. 95°C
because zeolite A is metastable and tends to transform leads to reasonable rate and well-developed crystals.[23]
thermodynamically to more stable phases.
These results indicate that zeolite NaA should be syn-
3.3. Characterization of zeolite NaA
thesized within eight hours. In order to further confirm
the optimal crystallization time, the FE-SEM technique To study the physical properties of zeolite NaA obtained
was applied to investigate the morphologies of the at the optimum synthesis conditions, further
6 C. ZHOU ET AL.
Figure 3. (a) XRD patterns of the synthesized products obtained at different molar ratios; FE-SEM images of the synthesized products
obtained at different molar ratios of SiO2/Al2O3 (b) 1.0, (c) 1.8, (d) 3.0 and (e) 4.2.
characterizations were carried out by FE-SEM/EDX, FT-IR exhibits the typical bands of characteristic value of
and calcium ion exchange capacity and whiteness zeolite NaA. The typical bands of NaA zeolite represent-
measurement. Well-defined edge of the zeolite NaA par- ing the asymmetric and symmetric stretch (1003 cm−1),
ticles in 1–2 µm with cubic crystalline structure is shown double rings (559 cm−1) and T (Al, Si)–O bend (667 and
Environmental Technology
in Figure 1(e). With the same time, EDX spectra and 466 cm−1) are observed. The appearance of the band
chemical composition of the selected area are presented at 1648 cm−1 could be assigned to the presence of the
in Figure 1(e1). Strong peaks of Na, Al, Si and O are clearly H2O mode and incomplete dehydration of the zeolite
emerged in the EDX spectrum and no other impurities samples because of the ν (H–OH–) vibration band.[24]
are detected in the spectrum, confirming high purity of Moreover, the observed single strong band at 3442
the zeolite NaA. According to the chemical composition cm−1 ascribed to the hydroxyl-groups. The data obtained
obtained from the EDX analysis, the molar ratio of Na2O/ from FT-IR spectra are consistent with reported values of
Al2O3/SiO2 is calculated to be 1:1.19:2.54, which is close the zeolite LTA synthesized from kaolinite [25] and NaA
to the theoretical formula of Na2O·Al2O3·2SiO2·4.5H2O. zeolite synthesized from halloysite.[26]
To confirm the structure of zeolite NaA, FT-IR spec- The effect of the concentration of NaOH solution on
troscopy was carried out, as shown in Figure 5(b). It yield and whiteness of synthesized zeolite are presented
Figure 4. (a) XRD patterns of the synthesized products obtained at different crystallization times; FE-SEM images of the synthesized
products obtained at different crystallization times (b) 0 h, (c) 2 h, (d) 4 h and (e) 8 h.
ENVIRONMENTAL TECHNOLOGY 7
Figure 5. (a) XRD patterns of the synthesized products obtained at different crystallization temperatures and (b) FT-IR spectrum of as-
synthesized zeolite NaA obtained from secondary CFA.
Table 2. Effects of NaOH addition, NaAlO2 addition, crystallization time and temperature on yield and whiteness of zeolite
produced.
Experiment NaOH (g/g ash) NaAlO2 (g/g ash) Crystallization time (h) Crystallization temperature (°C) Yield (g/g ash) Whiteness (%)
ZC1 0.4 1.58 95.16
ZC2 0.8 1.54 95.45
Environmental Technology
in Table 2. It shows that the yield is highly sensitive to syn- (1) and (2), the calcium ion exchange capacity of zeolite
thesis condition, since the crystallization parameters NaA synthesized at optimal conditions is calculated to
greatly affect the types of zeolites. Yield of up to a be 309 mg CaCO3/g, which is much higher than the stan-
maximum of 1.54 g/g of ash was produced for zeolite dard required in QB/T 1768-2003 (≥295 mg CaCO3/g). The
NaA from secondary CFA residue, which is much higher results indicate that the SCFA-prepared zeolite NaA
than the previous literature reported.[7] While it seems samples could be used as a builder in detergents (Table 3).
that the zeolization environment had almost no influence
on the whiteness, the whiteness is well above 95%, satisfy-
4. Conclusion
ing the requirement in QB/T 1768-2003 (whiteness ≥ 95%).
Calcium ion exchange capacity was measured to The present investigation showed that the secondary CFA
examine the adsorption property. According to Equations residue could be successfully converted to zeolite NaA
8 C. ZHOU ET AL.
with the preparation method reported in this paper. The [8] Blissett RS, Rowson NA. A review of the multi-component
optimal synthetic parameters for zeolite NaA synthesis utilisation of coal fly ash. Fuel. 2012;97:1–23.
[9] Querol X, Umana J, Alastuey A, Ayora C, Lopez-Soler A,
were obtained by a batch of experiments, and the well-
Plana F. Extraction of soluble major and trace elements
defined edge of the NaA zeolite with cubic crystalline from fly ash in open and closed leaching systems. Fuel.
structure was obtained at 2 mol/L NaOH, under the 2001;80:801–813.
SiO2/Al2O3 molar ratio of 1.8, after the hydrothermal treat- [10] Li Y, Wang Y, Gao Y, Zhong J. Study on properties of
ment at 95°C for 8 h. Furthermore, it was found that the hollow glass bead from fly ash. J Chin Ceramic Soc.
types of zeolites obtained were to be highly dependent 2002;30:664–667.
[11] Matjie R, Bunt J, Van Heerden J. Extraction of alumina from
on the synthesis parameters, other types of zeolites also
coal fly ash generated from a selected low rank bitumi-
could be synthesized by varying the parameters. The nous South African coal. Miner Eng. 2005;18:299–310.
calcium ion exchange capacity of zeolite NaA synthesized [12] Li L, Zhai Y, Wu Y, Liu Y, Wang J. Extracting alumina from
at optimal conditions is calculated to be 309 mg CaCO3/g fly ash by sulfuric acid. Light Met. 2006;12:9–12.
and the whiteness is over 95%, which satisfy the require- [13] Yao Z, Xia M, Sarker PK, Chen T. A review of the alumina
recovery from coal fly ash, with a focus in China. Fuel.
ment for being used as detergent, indicating a promising
2014;120:74–85.
future. The method used in this work could offer an [14] Qi L, Yuan Y. Characteristics and the behavior in electro-
advantage for large-scale industrial production of zeolite static precipitators of high-alumina coal fly ash from the
NaA for abundant and cheap raw material. Jungar power plant, Inner Mongolia, China. J Hazard
Mater. 2011;192:222–225.
[15] Tanaka H, Fujii A, Fujimoto S, Tanaka Y. Microwave-
Disclosure statement assisted two-step process for the synthesis of a single-
phase Na-A zeolite from coal fly ash. Adv Powder
No potential conflict of interest was reported by the authors. Technol. 2008;19:83–94.
[16] Hui K, Chao C. Effects of step-change of synthesis temp-
erature on synthesis of zeolite 4A from coal fly ash.
Environmental Technology